Disperse monoazo dyestuffs



United States Patent Office 3,341,513 Patented Sept. 12, 1967 3,341,513 DISPERSE MONOAZO DYESTUFFS Hans E. Wegmuller and Werner Bossard, Riehen, and Jacques Voltz and Francois Favre, Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland No Drawing. Filed Aug. 7, 1963, Ser. No. 300,670 Claims priority, application Switzerland, Aug. 2, 1962, 9,258/62 6 Claims. (Cl. 260-156) This application is a continuation-in-part of our copending application, Ser. No. 296,502, filed July 22, 1963 (now abandoned).

The present application concerns new, water-dispersible azo dyestuffs, processes for the production thereof, processes for the dyeing of organic hydrophobic material using the new dyestuffs and, as industrial product, the materials dyed with the aid of these dyestuffs.

Dyeing of organic hydrophobic fibrous materials such as high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, synthetic polyamide fibers and the like with the known disperse dyes are frequently not sufficiently fast; in particular, they often lack sufficient light fastness and fastness to sublimation, and the known disperse dyes lack drawing power on these materials.

It has now been found that compounds of the formula wherein A represents unsubstituted phenyl or lower alkylphenyl, trifiuoromethylphenyl, lower alkoxyphenyl, lower alkanoylaminophenyl, benzoylaminophenyl, nitrophenyl, cyan-ophenyl, fluorophenyl, chlorophenyl, bromophenyl, lower alkylcarbonylphenyl, benzoylphenyl, carbamylphenyl, mono-N-lower alkyl-carbamylphenyl, di-(N-lower alkyl) carbamylphenyl, N lower alkyl-N-phenyl-carbamylphenyl, piperidino (1)-carbonylphenyl, morpholino (l)-carbonylphenyl, lower alkoxycarbonylphenyl, phenoxy-carbonyl-phenyl or benzyloxy-carbamyl-phenyl, but no unsubstituted or N-substituted sulfamylor alkylor arylsulfonyl-phenyl radicals;

B represents hydrogen, alkyl with from 1 to 6 carbon atoms, cycloalkyl with from 5 to 6 carbon atoms, hydroxyalkyl with from 1 to 4 carbon atoms, cyanoalkyl with from 1 to 4 carbon atoms, alkoxyalkyl with a total of from 3 to 6 carbon atoms the alkyl moiety of which radicals contains at least 2 carbon atoms, phenyl-lower ,alkyl, lower alkyl-phenyl-lower alkyl, chloro-phenyl-lower alkyl, bromo-phenyl-lower alkyl, phenyl, lower alkylphenyl, chloro-phenyl, bromo-phenyl, lower alkoxyphenyl, lower alkanoylamino-phenyl, naphthyl, lower alkyl-naphthyl, chloro-naphthyl or bromo-naphthyl, and

R represents one of the following radicals: primary alkyl with from 4 to 10 carbon atoms, secondary alkyl with from 4 to 10 carbon atoms, phenyl, lower alkylphenyl, lower alkoXy-phenyl, chloro-phenyl, bromophenyl, lower alkanoylamino phenyl, hydroxy-lower alkybphenyl, carbamyl-phenyl, mono-N-lower alkylcarbamyl phenyl, di (N-lower alkyl)carbamyl-phenyl, lower .alkoxy carbonylphenyl, nitrophenyl, di (lower alky1)-arnino-phenyl, phenoXy-phenyl, lower alkyl-phenoxyphenyl, lower alkoXy-phenoxy-phenyl or pyridyl- (3) radicals; while cyclohexyl, chloro-phenoxy-phenyl, bromo-phenoxy-phenyl and phenyl-lower alkyl are second 2 choice as substituents R, wherein the substituent -SO -OR is bonded directly to a benzene or a naphthalene nucleus in Formula I, and which compounds of Formula I are free from Water-solubilizing groups which which dissociate acid in water, are highly useful as disperse dyestuffs for the dyeing of hydrophobic, synthetic organic textile fibers from aqueous dispersion e.g. for the dyeing of cellulose di-or tri-acetate, particularly however, for the dyeing of high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, e.g. of polyglycol terephthalates such as Terylene, Dacron, Tergal, or Trevira. Dyestuffs according to the invention are also useful for the dyeing of synthetic polyamide fibers such as nylon or of Perlon which dyeings are distinguished by their good fastness properties, among them fastness to washing (alkali, water, sea water, etc.) and to light and sublimation.

Moreover, light fast dyeings are obtained with the dyestuffs according to the invention on polyacrylonitrile fibers such as Orlon.

Dyestuffs of Formula I are also suited for use in dyeing acetate rayon, polyester fibers, polyamide fibers such as nylon and the like, in the mass, prior to spinning (dope dyeing) and also as pigments in lacquers and paints, because of their good solubility in organic solvents such as acetone, chloroform and the like.

Polyester fibers are dyed with aqueous dispersions of dyestuffs according to the invention preferably at temperatures of over C. under pressure. Dyeing can also be performed, however, at the boiling point of the dyebath in the presence of carriers such as phenylpenol, polychlorobenzene compounds or similar auxiliaries, or by the foulard process after which the dyeing is thermofixed at -210" C.

The drawing power of the dyestuffs can be still further improved by mixing two or more monoazo dyestuffs according to the invention.

Dyestuffs according to the invention are distinguished by good affinity to hydrophobic polyesters fibers, particularly to polyglycol terephthalates and, depending on their composition, produce on these fibers greenish yellow to reddish yellow dyeiugs of good colour strength which have very good fasteness to washing, sublimation, light, perspiration and cross-dyeing. In addition, vegetable and animal fibers, particularly cotton, are very well reserved by the dyestuffs according to the invention. They can also be dyed evenly with the usual commercial carriers.

Particularly satisfactory disperse dyestuffs which dye fast and with superior drawing power on the above-mentioned fibers, especially on polyethyleneglycol terephthalate fibers (cg. Dacron), are the compounds of the formula wherein B and R have the meaning given above,

'9 A is one of the radicals of the formulas S|O2-O R SOT-OR X X4 l X represents hydrogen, lower alkyl, lower alkoxy, Cl,

Br, -NO or CN, X represents hydrogen, lower alkyl, lower alkoxy, Cl,

Br, F, or --NO X, represents hydrogen, Cl, Br, CF or lower alkoxy-carbonyl, each of X and X independently, represents hydrogen,

lower alkyl, -Cl, Br, or NO and B represents phenyl, lower alkyl-phenyl, chloro-phenyl, bromo-phenyl, lower alkoxy-phenyl, lower alkanoylamino-phenyl, naphthyl, lower alkyl-naphthyl, chloro-naphthyl, or bromo-naphthyl,

the radical -SO OR in Formula III being directly bonded to a benzene or naphthalene nucleus, of B and the compounds of Formulas II and III being free from water-solubilizing groups which dissociate acid in water. Disperse dyestuffs with similar good proportion as those described in the foregoing, are those of the formula @N=N-N=NCCCH;|

HO- J I I (SOBOR) Y2 Yr r N is (1v) wherein Y represents hydrogen, lower alkyl, lower alkoxy, or hydroxy-lower alkoxy,

Y represents hydrogen, lower alkyl, lower alkoxy, hydroxy-lower alkoxy, chlorine, bromine, fluorine or trifluoromethyl,

and B and R have the above given means, and wherein the substituent SO OR is directly bonded to an aromatic nucleus in Formula IV, i.e. either a benzene nucleus or a naphthalene nucleus,

the compounds of Formula 1V being free from watersolubilizing groups which dissociate acid in water. Dyeings on the above-described hydrophobic fibers which have optimal fastness to light and sublimation are obtained with those disperse dyestuffs according to the invention which fall under the formula 4 wherein X represents hydrogen, chlorine, bromine, lower alkyl or lower alkoxy, X represents hydrogen,

or lower alkoxy, B represents phenyl, lower alkyl-phenyl, chloro-phenyl,

or bromo-phenyl, and R represents phenyl, lower alkyl-phenyl, lower alkoxyphenyl, chl'oro-phenyl, bromo-phenyl, hydroXy-lower alkyl-phenyl, lower alkanoylamino-phenyl, lower alkoxy-carbonyl-phenyl, carbamyl-phenyl, monoand di- (N-lower alkyl)-carbamyl-phenyl, or pyridyl-(3). The substituent -SO OR in the compounds of For mula V being bonded directly to the benzene nucleus in B and the said compounds being free from water-solubilizing substituents which dissociate acid in water.

The term lower in connection with aliphatic radicals means that these radicals have from 1 to 4 carbon atoms. Similar results are obtained with compounds of Formula V in which A represents or 01 Cl or oi preferably 2,4,6-trichlorophenyl.

The novel dyestuffs according to the invention are produced by coupling the diazonium compound of an amine of the formula chlorine, bromine, lower alkyl A-NH (V with a coupling component of the formula OH-GCH3 Holt i of which two reactants either the diazo compound or the coupling component contains a substituent SO OR, bonded directly to an aromatic (benzene or naphthalene) nucleus; A, B and R in Formulas VI and VII having the above given meanings.

In one group of coupling components which are suitable for use in the above reaction, B in Formula VII is either an aliphatic or a cycloaliphatic radical such as the methyl, ethyl, propyl, isopropyl, butyl, methoxypropyl, or cyanoethyl group or the cyclohexyl radical. When B is an araliphatic radical, it is, for example, the benzyl group; when it is an aromatic radical, it is, for example, an unsubstituted or a substituted phenyl or naphthyl radical.

In the substituent SO OR, the radical -OR represents, for example, an alkoxy group which is derived from nor sec. butanol, or from a primary or secondary amyl or hexyl alcohol, or it is a cycloalkoxy group, e.g. the cyclohexyloxy radical, or an unsubstituted or substituted aryloxy group which is derived, e.g. from a hydroxynaphthalene such as a l-hydroxyor 2-hydroxy-naphthalene or preferably from a monohydroxybenzene such as phenol, an alkyl-, alkoxy-, or hydroxyalkyl-hydroxybenzene, or an aryloXy-, halogeno-, dialkyl-amino-, N- al-kyl-N-phenylamino-, alkoxycarbonyl-, carbamyl, or alkanoylamino-hydroxybenzene, i.e. it is derived, for example, from 2-, 3- or 4-methylor 2-, 3- or 4-ethyll-hydroxybenzene or technical mixtures thereof, from 3,4- or 2,4-di methyl-, 4-sec. butyl-, 4-iso0ctyl-, 2-, 3- or 4-chloro-, 2,4-dichloro-, 2-, 3- or 4-methoxy 2-, 3- or 4-ethoxy-, 4- phenoxy-, 3-dimethylamino-, 3-diethylamino-, 2,4-dicarbomethoxyor 2,4-di-carboethoxy-l-hydroxybenzene, 2- hydroxymethyl-l-hydroxybenzene, 2 acetylaminol-hydroxybenzene or 3-acetylamino-l-hydroxybenzene.

Examples of substituents of the benzene ring of A are: aliphatic groups such as methyl, trifluoromethyl, ethyl, propyl or isopropyl groups, alkoxy groups such as methoxy, ethoxy or butoxy groups, acylamino, especially lower alkanoylamino groups such as acetylamino, or benzoylamino groups, particularly however, electrophilic substituents such-asnitro groups, the trifluoromethyl or cyano groupsmentioned above, halogens, in particular fluorine, chlorine or bromine, keto groups such as acetyl, propionyl or benzoyl groups, and, when the substituent SO -OR is at the B-moiety, carboxylic acid ester groups such as the carbomethoxy, carboethoxy, carboisopropoxy, carbobutoxy, or carbophenoxy group, or unsubstituted or substituted carbamyl or sulfamyl groups.

, In the compounds in which ring A contains an arylazo group, the latter is preferably a phenylazo group the benzene ring of which is unsubstituted or contains the substituents previously mentioned. In the compounds of Formula I in whichB presents an araliphatic or an aromatic radical, the rings of that radical are either unsubstituted or substituted, for example, by halogens such as chlorine or bromine, particularly in a position adjacent to the bond to the pyrazolene nucleus as well as by lower alkyl or alkoxy groups or acylamino, especially lower alkanoylamino groups.

Dyestuffs of Formula I substituted at the benzene ring of A by an arylazo group produce more reddish yellow dyeings; when A does not contain an arylazo group, very pure, more. greenish yellow dyeings are obtained.

When diazonium compounds of amines of Formula VI usable according to the invention contain the characteristic SO OR group, then these are, for example, esters of the alcohols, naphthols and, particularly, phenols mentioned above in the discussion of the group RO-, which are derived, forexample, from l-aminobenzene-Z, -3- or -4-sulphonic acid, 2-alkyl-l-aminobenzeneor 2-halogenl-aminobenzene- -4- or 5-sulphonic acids, 3-alkyl-l-aminobenzene-j l-sulfonic acid, 4-alkyl-l-aminobcnzeneor 4- halogen-l-aminobenzene- Z-sulphonic acids, or 2,5-dichloro-l-aminobenzene-4-sulphonic acid, 3,4-dichloro-laminobenzene-6-sulfonic acid and 2-chloro-3-1nethyl-l-aminobenzene-6-sulfonic acid.

Coupling components of Formula VII usable according to the invention which contain the SO OR group as defined are esters of the hydroxyl compounds mentioned with, e.g. lphenyl-3-methyl-pyrazol-5-one, 2'-, -3'- or -4- sulphonic acid, 1-(4'-methyl-phenyl)-3 methyl-pyrazole- 5-one-3'-sulphonic acid, 1 (2-chloro-phenyl)-3-methylpyrazol-5-one-5'-sulphonic acid, 1-(2',5'-di-chlorophenyl)- 3-methyl-pyrazol-5-one-4'-sulphonic acid.

Amines of Formula VI containing sulphonic acid ester groups are obtained, for example, by reacting the desired alcohol, naphthol or phenol with the corresponding nitrobenzene sulphonic acid chloride or bromide and then reducing the nitro group to the amino group.

Sulfonic acid ester substituted pyrazolones of Formula VII which serve as coupling components for producing dyestuffs according to the invention are produced by esterification of the corresponding starting compound of the formula wherein B has the above given meaning, with the corresponding hydroxylated compound of the formula wherein R has the meaning given above, reduction of the nitro group of the resulting nitro ester to the corresponding amino ester, conversion to the hydrazino ester and condensation of thelatter with an acetoacetic acid ester.

Examples of amines of Formula VI free from the characteristic sulphonic acid ester group which are used according to the invention are l-amino-Z-nitrobenzene, 1-amino-2 nitro-4-methyl-benzene, 1-amino-2-nitro-4-methoxyor 4-ethoxy-benzene, 1-amino 2-nitro-4-chloro-,

-4-fluoroor -4-bromo-benzene, l-amino-2-nitro-4-trifluoromethyl-benzene,

6 1-amino-4-nitrobenzene, 1-amino-4-nitro-2-methylbenzene, 1-amino-4-nitro-2-methoxyor -2-ethoxy-benzene, 1-amino-4-nitro-2-chloro-,

-2-fluoroor -2-brorno-benzene, 1-amino-4-nitro-2-cyanobenzene, l-amino-4-nitro-2,5-di-chlorobenzene, 1-amino-4-nitro-2,6-dichloroor -dibromo-benzene, l-amino-2,4-dinitrobenzene, 1-amino-2-4-dinitro-6-chlorobenzene or l-amino-2,4-, -2,5- or 3,4-dicyanobenzene, 4-nitro-3-carbethoxy-l-amino-benzene, 4-nitro-2-carbethoxy-1-amino-benzene, l-amino-Z-chlorobenzene, 1-amino-3-chlorobenzene, l-amino-4-chlorobenzene, 1-arnino-2,4-chlorobenzene, 1-arnmo-2,5-dichlorobenzene, 1-amino-3,4-dichlorobenzene, 1-amino-2,6-dichlorobenzene, 1-amino-2,4,S-trichlorobenzene, 4-amino-azobenzene, 4-amino-2', 3-dimethyl-azobenzene, 4-amino-2,5-dirnethoxy-3-methy1-azobenzene, 4-amino-2-methyl-5-methoxy-4'-hydroxyethoxyazobenzene and 4-amino-2-methyl-5-methoxy-3'-hydroxyethoxyazobenzene.

, Examples of coupling components of Formula II without the defined SO OR group are 3-methyl-pyrazol-5- one, 1,3-dimethyl-pyrazol-5-one, 3-methyl-pyrazol-5-one which are substituted in l-position by ethyl, propyl, isopropyl, ,e-hydroxyethyl, ,B-cyanoethyl, cyclohexyl, benzyl, phenyl, 2'-methyl-phenyl, 3-methyl-phenyl, 4'-methylphenyl, 2'-methoXy-phenyl, 3-methoxy-pehnyl, 4'-methoxy-phenyl, 2'-chloro-phenyl, 4'-chloro-phenyl, 2',4-dichloro phenyl, 2,4' dibromo-phenyl, 3'-acetyl-aminophenyl or 4-acetyl-amino-phenyl.

The coupling is performed in mineral acid or, preferably, in weakly acid solution advantageously, while gradually bulfering the acid, e.g., with alkali metal salts of carbonic acid or low fatty acids. If desired, a suitable diazonium compound can also be coupled simultaneously with a mixture of two or more coupling components which are usable according to the invention.

A modification of the process for the production of azo dyestuffs consists in condensing an azo compound of formula wherein A represents a phenyl radical which can also contain phenyl azo groups,

B represents hydrogen or an aliphatic, cycloaliphatic,

or aromatic radical,

X represents chlorine or bromine and the SO -X group is directly bound to an aromatic, carbocyclic nucleus,

with an organic hydroxyl compound of formula wherein R represents an alkyl radical containing at least 4 carbon atoms or a cycloalkyl radical or an unsubstituted or a substituted aryl radical,

to form the corresponding compound of Formula I, the components being so chosen that the resulting dyestufl" does not contain any water-solubilizing groups which dissociate acid in wate Naturally, the remarks regarding A, B and --S0 -OR in the first process also apply to this process variation.

The starting materials of the Formula VIII are obtained, for example, by coupling the diazonium compound of an amine of Formula V1 with a coupling component of Formula VII, one of which components contains the sulfonic acid group, directly bound to an aromatic, carbocyclic nucleus, and converting the azo dyestuff sulfonic acid so obtained to the corresponding sulfonic acid chloride, or bromide, for example by means of a phosphorus halide or thionyl chloride, without or in the presence of a tertiary nitrogen base and an inert solvent or diluent. Examples of suitable amines of Formula VI and of coupling components of Formula VII are the l-aminobenzenes or 3-methyl-pyrazol-5-ones respectively or the sulfonic acids of these compounds mentioned in the first process, as well as Z-nitro-l-aminobenzene 4-sulfonic acid, 4-nitro-l-amino-benzene-Z-sulfonic acid, 5 chloro-2-nitro-1-amino-benzene-4-sulfonic acid, 4-amino-azobenZene-4-sulfonic acid, 2-methyl-4- amino-azobenzene-4-sulfonic acid and 2-methyl-4-aminoaZobenzene-3'-sulfonic acid.

Examples of organic hydroxyl compounds of Formula IX which are to be reacted with the sulfonic acid chlorides or bromides of Formula VIII are those mentioned in the illustration of RO.

The condensation of compounds of Formula VIII with the hydroxyl compounds of Formula IX to form esters of Formula I is performed advantageously at a raised temperature, optionally in aqueous, organic or aqueous/ organic solution. Suitable organic solvents for this purpose are those which are miscible with water, e.g., lower alkanols, especially methanol or ethanol, lower aliphatic ketones such as acetone or methylethyl ketone, or ether alcohols such as ethylene glycol monomethyl or monoethyl ether, or those which are not miscible with water, e.g., unhalogenated or halogenated aromatic hydrocarbons such as benzene, toluene, xylenes, chlorobenzene or dichlorobenzenes. The hydroxyl compounds to be reacted, such as the hydroxyalkyl, hydroxycycloalkyl or hydroxyaryl compounds, are advantageously used in the form of their metal salts such as the sodium or potassium salts.

The following non-limitative examples illustrate the invention. Where not otherwise expressly stated, parts and percentages are by weight. The temperatures are in degrees centigrade. The relationship of parts by weights to parts by volume is as that of grams to cubic centimeters.

EXAMPLE 1 34.4 parts of 1-phenyl-3-methyl-pyrazole-5-one-3'-sulphonic acid-(4"-methylphenyl)-ester are dissolved in 100 parts of dimethyl formamide and the solution is poured into 400 parts of water and 6 parts of cetyl polyglycol ether while stirring quickly. The diazonium salt solution of 17.3 parts of l-amino-2-chloro-4-nitro-benzene is added dropwise at 05 to the fine dispersion and then the free mineral acid is buttered by the addition of sodium acetate. On completion of the coupling, the precipitate formed is filtered oif, washed with a great deal of water and dried in vacuo at 60-70. The coupling product is a red-orange powder, the composition of which corresponds to the formula Milled with a condensation product of naphthalene sulphonic acids and formaldehyde, the dyestufr so obtained dyes polyglycol terephthalate fibres such as Dacron in vivid yellow shades from aqueous dispersion, if necessary in the presence of carriers such as o-phenylphenol. The

bath is substantially exhausted. The dyeings have excel-. lent fastness to washing, sublimation and light.

The 1-phenyl-3-methyl-pyrazole-5-one 3' sulphonic acid- (4"-methylphenyl)-ester used for the coupling is ob-v tained for example by reacting 1-nitrobenzene-3-sulphonic acid chloride with p-cresol, reducing the nitro group to the amino group, converting the l-aminobenzene-Bf-sul: phonic acid-(4-methylphenyl)-ester into the corresponding hydrazine and condensing the 1-hydrazino-benzene-3- sulphonic acid-(4"-methylphenyl)-ester with acetoacetic acid methyl ester.

If, instead of the 34.4 parts of 1-phenyl-3 -rnethylpyrazole-5-one-3sulphonic acid (4" methylphenyl)- ester, a corresponding amount of the coupling components given in Table I is used and they are coupled under the conditions given in the above example, then dyestuffs are obtained which produce dyeings on polyester fibres which have equally good properties.

TABLE I Shade on polyester fibres Diazo component Coupling component 1-arnino-4-nitro-2- chlorobenzene.

l-pheny1-3-methyl-pyrazo1e-5- Yellow.

one-3-sulphonic acid phenyl ester. 1-phenyl-S-methyl-pyarzole-S- one-3-sulphonio acid- (2"- methylphenyD-ester. l-phenyl3-methyl-pyrazole-5- one-3-su1phonic acid- (3- methylphenyl)-ester. I 1-phenyl-3-methyl-pyrazole-5- one-3-sulphonic acid- (2- chlorophenyD-ester. l-phenyl-3-methy1-pyrazo1e-5- one-3-sulphonie riled-(4- ehlorophenyD-ester. 1-phenyl-3-methyl-pyrazole-fione-3-sulphonic acid-( dichlorophenyD-ester. 1-phenyl-3-methyl-pyrazo1e-5- one3-sulphonie acid-(3- methoxyphenyD-ester. 1-phenyl-3-methyl-pyrazo1e-5 one-3-sulphonic acid- (4- tert.butylphenyl)-ester. I-phenyl-3-methyl-pyrezole-e one-3-su1phonic acid- (4"- carboethoxyphenyD-ester. l-phenyl-3-methyl-pyrazole-5- one-3-sulphonic acid-(4- phenoxypheny1)-easter.

EXAMPLE 2 After milling with a condensation product of naphthalene sulphonic acids and formaldehyde, it dyes polyglycol terephthalate fibres such as Dacron in reddish yellow shades from an aqueous dispersion, sometimes in the presence of o-phenylphenol. The dyeings have excellent fastness to washing, light and sublimation.

The 1-phenyl-3-methyl-pyrazole-5-one 4 sulphonic acid phenyl ester used as starting material is obtained by reacting l-nitrobenzene-3-sulphonic acid chloride with phenol, reducing the nitro group to the amino group, converting the amine into 1-hydrazino-benzene 3 sulphonic acid phenyl ester and condensing this with acetoacetic acid methyl ester.

Dyestuffs having similar properties are obtained if, instead of the 33.0 parts of 1-phenyl-3-me-thyl-pyrazole-5- one-4-sulphonic acid phenyl ester, the equivalent amounts of 1-phenyl-3-methylpyrazole-5-one-4 sulphonic acid- (2"- methylphenyl)-ester, l-phenyl-3 methylpyrazole one-4-sulpho'nic acid-(3"-methylphenyl) ester, l-phenyl- 3-rnethylpyrazole-5-one-4'-sulphonic acid-(4" methylphenyl)-ester or 1-phenyl-3-methylpyrazole 5 one 4'- sulphonic acid (2" chlorophenyl) ester, 1 phenyl- 3-methylpyrazole 5 one 3 sulphonic acid (2"- methy1phenyl)-ester or 1-phenyl-3-methylpyrazole S-one- 3-sulphonic acid phenyl ester, 1-phenyl-3-methylpyrazole- 5-one-3'-sulphonic acid-(2"-chlorophenyl)-ester are used.

EXAMPLE 3 Nitrosyl sulphuric acid, corresponding to 6.9 parts of sodium nitrite, is slowly added dropwise to a solution of 16.3 parts of 1-amino-4-nitro-2-cyanobenzene in 100 parts of concentrated sulphuric acid and the reaction mixture is kept for 3 hours at room temperature. The solution of the diazonium salt so obtained is then poured into a slurry of 36.5 parts of 1-(2'-chlorophenyl)-3-methylpyrazole-5-one-5'-sulphonic acid- (4-methylphenyl) -ester and 120 parts of crystallised sodium acetate in 150 parts of dirnethyl formamide and 1500 parts of ice water whereupon the yellow azo dyestulf of the formula precipitates. The pH of the coupling solution is maintained at 4-5 by the simultaneous addition dropwise of sodium hydroxide solution. On completion of the coupling, the dyestufi is filtered off, washed neutral with Water and dried in vacuo at 60-70".

The l-(2'-cl1lorophenyl) 3-methylpyrazole-5-one-5'- sulphonic -acid-(4"-methylphenyl)-ester used as coupling component is obtained analogously to the coupling component mentioned in Example 2 starting from 4-nitro-2- chlorobenzenes-S-sulphonic acid chloride and p-cresol.

A dyestufl preparation milled with the condensation product of naphthalene sulphonic acids and formaldehyde which contains the dyestulf in fine distribution dyes polyglycol terephthalate fibres such as Terylene in pure greenish yellow shades from an aqueous dispersion, sometimes in the presence of carriers. The dyeings have excellent fastness to washing, rubbing and sublimation.

If in the above example, instead of the 16.3 parts of 1-amino-4-nitro-2-cyanobenzene, corresponding amounts of the amines given in the following Table II are used and these are coupled under the conditions described in the example with the corresponding amount of a pyrazolone derivative given in column 3, then dyestufis are obtained which produce dyeings on polyester fibres having equally good properties.

TABL 11 Shade on No. Diazo component Coupling component polyester fibres 5 1.-. l-amino-Z nitro 1(2'-cl1lorppheny1)B-methyl- Greenish benzene. pyrazole-5 one-5-sulphonic yellow.

acid phenyl ester. 2--. 1-annno-3-n1tro- .do Do.

benzene. 3--. 1-amlno-4-nitro- 1-phenyl-3-methy1pyrazole-5- Yellow. 10 benzene. one-3-sulphonic acid-(3- methylphenyD-ester.

4... do 1-(2-eh1orophenyl)-3-methyl- Greenish pyrazole-5-0ne-5-sulphonic yellow. aetid- (4-methylphenyl)- es er.

5.-. 1-arnino-2-nitro-4- 1-phenyl-3-methylpyrazolet Yellow. methylbenzene. one3-sulphonic acid- (2- methylphenyD-ester.

6--. do 1-phenyl-3-methylpyrazole-5- Do,

one-4-sulphonie acid-(4- nethylphenyD-ester 7 1-ammo-4-n1tro-2- 1-(2-chloropheny1)-3-methyl- Greenisli chlorobenzene. pyrazole-fi-one-fi'rsulphonie Yellow. acid-( -methylphenyl)- ester.

8 ,do 1-phenyl-3-methylpyrazole-EF Yellow.

one-#sulphonic acid-(4- methylphenyllester.

9--. 1-amino-4-nitro-2- l-phenyl-iimethylpyrazole-5- 'Do.

bromobenzene. onte-3-sulphonic acid phenyl es er 10-- 1-amino-4-nitro-2, l-phenyl-3-methylpyrazole-5- Do.

fi-dichloroone-3-su1phonic acid-(4- benzene. methylphenyl)-ester. 11;- 1-amino-2-nitro-4- l-phenyl-3-methylpyrezole-5- D chlorobenzene. one-4-sulphonic acid-(2- methylphenyl)-ester. 12.- 1-amino2,4-dil-phenyl-3-methylpyrazole-5- Do.

nitrobenzene. one-3-sulphonic aied-(4- methylphenyD-ester.

13.- do 1-phenyl-3 methylpyrazole-5- Do.

one-4-sulphonic acid-(4- tert.butylphenyl)-ester.

nitro-2-ch1oroonet sulphonic acid- (2 benzene. methylphenyl)-este:r. 15-- do l-phenyl-3 rnethylpyraz0le-5- Do,

one-3-sulphonie acid-(4 carboethoxyphenyllester. 16-. 1-am1no-4-n1tro-2- l-phenyl-3-methy1pyrazole-5- D0.

methoxybenone-3-sulphonic acid-(2"- zene. I chlorophenyl)-ester. 17-- 1-arnino-4-n1tr0-2- 1-(4-methylphenyl)-3-methyl- Greenish methoxybenpyrazole-5-one-3sulphonic yellow.

zene. acid-( -methy1phenyl)- es er.

18-. do 1 (2-chlorophenyl)-3-rnethyl- D0.

pyrazoleeone-5-sulphonic aeid-(4-methylphenyl)- ester. 19-- l-ammo-Z-nrtrol-phehyl-iZ-methylpyrazole-5- Yellow.

'methoxyone-4-sulphonie acid-(2- benzene. methylphenyD-ester.

20 do 1-(2'-chlorophenyl)-3-methyl- Greenish pyrazole-5-one-5-sulphonic yellow. acid-(4-methylphenyl)- ester.

EXAMPLE 4 15.1 parts of 1-arnino-2-nitro-4-methylbenzene are diazotised in the usual way and coupled with 28.8 parts of 1-(2-chlorophenyl) 3 methylpy-razole-5-one-3-sul phonic acid. The dyestuff so obtained is dried, and converted with phosphorus oxychloride in an inert solvent in the presence of catalytic amounts of pyridine; into the" corresponding sulphonic acid chloride.

7 parts of this dyestuff acid chloride, 4 parts of 4- chloro-l-hydroxybenzene and 14 parts of sodium carbonate in a mixture of 100 parts of Water and '30 parts of ethyl alcohol are boiled for I6 hours while stirring vigorously. After cooling the reaction mixture to room; temperature, the yellow dyestuff is filtered off, washed in a lot of water and dried in vacuo at 6l)-70. The product so obtained has the formula L N NO: HO LN A preparation produced by milling the dyestufr" with a condensation product of naphthalene sulphonic acids and formaldehyde dyes polyglycol terephthalate fibres such as Terylene or cellulose triacetate fibres in pure yellow shades from an aqueous dispersion, if necessary in the presence of carriers such as o-phenylphenol. The dyeings are fast to washing, sublimation and light.

EXAMPLE 5 then cooled to room temperature and the yellow dyestufl. corresponding to the formula is filtered olf and washed with a lot of water. The product when dried in vacuo at 60-70 is a yellow powder.

A preparation produced by milling the dyestuif with a condensation product of naphthalene sulphonic acids and formaldehyde dyes polyglycol terephthalate fibers such as Terylene or cellulose triacetate fibers in greenish yellow shade from an aqueous dispersion, sometimes in the presence of carriers such as o-phenylphenol. The dyeings are 20 fast to washing and sublimation.

If in the above example, instead of the 28 parts of the dyestulf acid chloride mentioned, corresponding amounts of the acid chlorides mentioned in the following table are used and they are coupled under the conditions described with one of the hydroxyaryl compounds given in column 3, then yellow dyes-tuifs are obtained which produce polyester dyeings having equally good dyeing properties.

TABLE III N o. Sulphonic acid chloride Hydroxyaryl compound Shade ofir polyester res l OH3ON=N HCHr kmethyl-l-hydroxybenzene Greenish yellow.

5 C N=N OH; 4-chloro-1-hydroxybenzene Do.

I0H O 3 HO N SO2C1 ClC -N=N CH3 lmethyl-l-hydroxybenzene- Do.

HO N

O1 C1ON=N H OH; Do.

i HO N OSOzOl TABLE III-Continued N o. Sulphonlo acid chloride Hydroxyaryl compound Shade g1]; polyester ms 19.. O NC N=N-ICH 4-carboethoxy-l-hydroxybenzene"in... Greenish yellow.

20--- ClN=N I CH 2-methyl l-hydroxybenzene Yellow. I ll 21..... OION=N CH3 l-hydroxybenzene Greenish yellow. V 1110 2 HO N 80101 22. OZN N=N CH 4-chloro-1-hydroxybenzene Do.

H 000 a) /N 'sbgoi 23-.- OzNQ :N I I CH 3-acetylamino-l-hydroxybenzene Yellow.

2 6 HO N/ O 24....- H 0 N=N'HCH; i 4-oh1oro-1-hydroxybenzene Greenish yellow. k N i V 2 Ho E SO2C1 EXAMPLE 6 E 5 tate. On completion of the coupling, the dyestuff of the formula A fine suspension of 13.7 parts of l-arnino-Z-nitrobenzone in 500 parts of water, parts of 36% hydrochloric N=N acid and 5 parts of cetyl polyglycol ether is diazotised in N the usual way at 5-7 by the addition of 6.9 parts of sodium nitrite. A solution of 38.0 parts of 1-(2-chlo1 ophenyl)-3-methylpyrazole-5-one-5'-su1phonic acid-(2"-1 nethyl- 01 CH8 phenyl)-ester in 125 parts of dimethyl formamide is added dropwise at 0-5 to the clear diazonium salt solution, and the mineral acid is buffered by the addition of sodium aceis filtered off, washed with water, dried in vacuo at 6070 and milled with a mixture of a condensation product of naphthalene-Z-sulphonic acid with formaldehyde and a lignin sulphonate. The dyestuff is a yellow powder which dyes polyglycol terephthalate fibres in pure greenish yellow shades from an aqueous dispersion if necessary in the presence of a carrier such as o-phenylphenol. The dyeings have very good fastness to washing, rubbing, light and sublimation.

The 1-(2'-chlorophenyl)-3-methylpyrazole-5-0ne-5'-sulphonic acid-(2"-methylphenyl)-ester used as coupling component is obtained, for example, by reacting l-nitro- 2-chlorobenzene-5-sulphonic acid chloride with o-cresol, reducing the nitro group to the amino group, converting the 1-amino-2chloro-5-sulphonic acid (2"-methylphenyl)- ester into the corresponding hydrazine and condensing this with acetoacetic acid methyl ester.

EXAMPLE 7 l N02 HO- l O 3 C a is filtered off and washed with a lot of water. After drying solvents, e.g. chloroform of acetone. The dyestuff can be used for the dyeing of lacquers, e.g. nitro lacquers or stoving lacquers, and for the dyeing of acetyl cellulose in the mass. Acetyl cellulose dyed therewith in the spinning mass has a pure yellow shade and has good wet fastness and very good light fastness properties.

The 1 phenyl 3-methyl-4-(2"-nitro-4"-chloro-pheny1- azo)-pyrazole-5-one-3-sulphonic acid chloride used as starting material is obtained by coupling diazotised 1- amino-Z-nitro-4-chlorobenzene with 1-phenyl-3-methylpyrazole-5-one-3'-sulphonic acid and reacting the dry dyestutf sulphonic acid with phosphorus oxychloride in chlorobenzene in the presence of catalytic amounts of pyridine.

EXAMPLE 8 17.3 parts of 1-amino-4-nitro-2chlorobenzene are diazotised analogously to Example 1 and coupled with 25.4 parts of 1 phenyl 3 methylpyrazole-5-one-3'-sulphonic acid. The dried dyestutf so obtained is converted into the corresponding sulphonic acid chloride with phosphorus oxychloride in an inert solvent in the presence of catalytic amounts of pyridine.

7 parts of this dyestuif acid chloride, 4 parts of 4-rnethyl-l-hydroxybenzene and 14 parts of sodium carbonate are boiled for 16 hours, while stirring vigorously, in a mixture of 100 parts of Water and 30 parts of ethyl alcohol. After cooling the reaction mixture to room temperature, the yellow dyestufi is filtered off, washed with a lot of water and dried in vacuo at -70". The product so obtained has the formula NO ON=N- CH 2- (5 I E 3 solo-Gen,

TABLE IV No. sulphonic acid chloride Hydroxyaryl compound Shade grlr) polyester 1 NOQC N=N' ILLCHI 2-methyl-l-hydroxybenzeue Yellow.

HO N

SO:C1

2 NOz-N=N CH1 4-chloro-l-hydroxybenzene Do.

i l a HO N SO1Cl TABLE IV Con'tinued No. Sulphomc acid chloride Hydroxyaryl compound Shade ofirli3 polyester res 17- ON=NON=N-HCH 2-methyl-l-hydroxybenzene Reddish yellow.

l 2 HO N 18--.- N=N- HCH3 4-chloro-l-hydroxybenzene. Yellow;

to l a 2 H0 N Osoml 19.--- N=N-"OH 3 aeetylamino-l-hydroxybenzene Do;

to l a 2 H0 N 20..-. C -N=N-CH 2-methyl-1-hydroxybeuzene Greenish yellow.

to I

i HO N 01 t EXAMPLE 9 60 l y N0 ;=N-- I on, J 3 z l I A dyestufi acid chloride 1s prepared by treating the dye- 01 H0 stufi obtained by coupling diazotised 1-amino-4-n1tro-2,6- N dichlorobenzenewith 1-(2',5-dich1orophenyl)-3-rnethy1- 65 pyrazole-S one-4 -sulphonic acid with phosphorus oxychlo- C1 ride in tetrachloromethane in the presence of catalytic amounts of N,Nsdimethyl aniline. 7 parts of this dyestuff acid chloride are slurried in 150 parts of water and 30 l parts of ethanol and, after the addition of 14 parts of 70 'Y sodium carbonate and 6 parts of 4-methyl-1-hydroxybenzene, the reaction mixture is boiled for 18 hours while stirring well. The precipitated dyestufi obtained after cooling the reaction frnass is washed with a lot of water and dried in vacuo at 60-70". It corresponds to the formula 5 terephthalate fibres such as Terylene in pure greenish 27 28 yellow shades from an aqueous dispersion, sometimes in given in the above example" if equivalent amounts of the the presence of carriers. The dyeings are fast to washing, sulphonic acid chlorides given in column 2 of the folrubbing and have excellent fastness to sublimation. lowing Table V are condensed with equivalent amounts of Similar dyestuffs are obtained under the conditions the hydroxyaryl compounds given in column 3.

TABLE V No. Sulphonlc acid chloride Hydroxyaryl compound Shade 31]; polyester res NOz-- N= oH3 4-methy1-1-hydroxybenzene Yellow.

" ('11 HO N 2 N O1-- N=N 'CHa 2 methyl-l-hydtoxybenzene Greenlsh yellow.

HO N

3--...- CH N=N-OH; 4-t.butyl-l-hydroxybenzene Yellow.

7 lo JL 9 a HO N Q-.." NO:-C -N=N u CH a I V I 4-methyl-l-hydroxybenzene D0.

5 NOr-C -N= -TCH3 3-methyl-I-hydroxybenzene Greenish yellow.

1&0 E0 N 0-4010! I CH3 6 NOi -N= CH 4-ch1oro-1-hydroxybenzene Yellow.

SOgCl 31 32 TABLE V-Continued No. Sulphonie acid chloride Hydroxyaryl compound Shade grgrpolyester 13... O-N=N- --N=NH-'CH; Z-aeetylamlno-l-hydroxybenzene Reddish yellow.

I H N SO:C1

l CH! 14" O-N= O- =N-TCH3 2-n1ethyl-l-hydroxybenzcne D0.

H0 N v -S0a0l 1 CH3 l 15..- HOOHzOHz0-N=N- N=N--HCH; 3-methyl-l-hydroxybenzene Do.

i N H0 N SOaCl a 16 ClC -N=N -N=N CH 2-hydroxymethyl-l-hydroxybenzene.. Do.

L H0 N (|)CH! 17-. CH;- -N= @N=N CH3 Hydroxybenzene Do.

OH l 8 H0 N -SO:C1

EXAMPLE with water and dried in vacuo. It corresponds to the 1-aminobenzene-3-sulphonic acid is diazotised in the known manner and coupled with l-phenyl-B-rmethylpyrazole-S-one. The dried azo dyest'ufi is converted into the corresponding dyestufi acid chloride in chlorobenzene with phosphorus oxychloride in the presence of a little pyridine as catalyst.

6 parts of Z-methyl-l-hydroxybenzene and parts of sodium carbonate are added to 10 parts of this acid chloride in a mixture of 120 parts of water and 40 parts of ethanol and then the reaction mass is boiled for 12 hours while stirring. After cooling the reaction mixture, the dyestuif formed is filtered off under suction, washed formula Q-o sog aw];-

A dye preparation milled with a naphthalene sulphonic acid/formaldehyde condensation product which contains the dyestulf in fine distribution, dyes polyglycol terephthalate fibres such as Trevira in pure yellow shades from an aqueous dispersion, sometimes in the presence of carriers such as o-phenylphenol. The dyeings are fast to washing, rubbing and light.

Dyestuifs having similar properties are obtained if, instead of Z-methyl-l-hydroxybenzene in the above example, the equivalent amount of 4-methyl-1-hydroxy- 34 benzene, 2-chloro-l-hydroxybenzene, 2,-4 dichloro-l-hydroxybenzene, B-methoxy-l-hydroxybenzene or 4-t.butyll-hydroxybenzene is used.

Similar dyestuffs are obtained under the above conditions if equivalent amounts of the sulphonicacid chlorides given in column 2 of the following table are condensed with the corresponding amounts of the hydroxyaryl compounds listed in column 3.

TABLEEVI N o. Sulphonic acid chloride Hydroxyaryl compound Shade E111) polyester res 1 O1SOg-N=N- TGH 4-methyl-1-hydroxybenzene Yellow.

l HO III 2 GI-SOlON=N CHI 4-t.butyl-1-hydroxybenzene Do.

L HO 3 CISO ON=N CH; 4-methyl-1-hydroxybenzene Greenish yellow.

4 N=N I 0H3 do Yellow.

I 1 l 80 O1 5 @N=NI|\LCHa 2.methyl-1-hydr0xybenzene D0.

so 01 L 2 HO N 6 Q-N=N -CH Z-chloro-l-hydroxybenzene Greenlsh yellow,

0 C1 2 HO N 1-aminobenzene-4-sulphonic acid is diazotised in the usual way and coupled with 3-rnethylpyraz0le-5-one. The dyestutf is Well dried and then converted into the corresponding dyestuff acid chloride with phosphorus oxychlo- TABLE VI-C0n tinued No. Sulphonic acid chloride Hydroxyaryl compound Shade or}; 1 pglyester 7 Ol0zS- N=NC N:N 0113 4-methyl-l-hydroxybenzene Reddish yellow.

8 Q JTT HO N 9 C102S- N=N'N:N H-OH 4-chl0ro-1-hydroxybenzene Do.

10 C1O2S- N=N- N=N H-GH3 Z-methyI-I-hydroxybenzene Do.

I 11 HaCC -N= H-CH Hydroxybenzene Yellow.

OCHa

12 ClOzS N=N-N= HCH Z-hydroxymethyl-l-hydroxybenzene. Reddish yellow.

CH l

3 HO III 1a ClOzS-C N=NC N= H-CHB Hydroxybenzene Do.

CHzCHzCN EIQMMPLE 11 ride in an inert solvent such as chlorobezene in the presence of catalytic amounts of pyridine. 24 parts of sodium carbonate and 11 parts of 4-amyl-l hydr-oxybenzene are added to a suspension of 12 parts of this acid chloride 75 in a mixture of 150 parts of water and 50 parts of ethanol,

A dye preparation milled with a naphthalene sulphonic acid/formaldehyde condensation product which contains the dyestufi i-n fine distribution, dyes polyglycol terephth'alate fibres such as Dacron in yellow shades from an aqueous dispersion, if necessary in the presence of a carrier such as o-phenylphenol. The dyeings have good dyeing properties.

Similar dyestulfs are obtained under the conditions described above if equivalent amounts of the sulphonic acid chlorides given in column 2 of the following table are condensed with the equivalent amounts of hydroxyaryl H compounds given in column 3.

TABLE VII No. Sulphonic acid chloride Hydroxyaryl compound Shade 31% polyester res 1 CIO2S*C N=N "-0113 4-methyl-1-hydr0xybenzene Greenish yellow,

l h HO 1? 2 CIO S N=N H-JJH; 4ch10r0-1-hydr0xybenzene Do,

HO I

CzHs

3 N=N'- IE-CEa 4-methyl-l-hydroxybenzene Do,

0 01 JL 2 HO N 4s.--" C1O S N==N ILL-43H; Hydroxybenzene Do.

HO N 5 QN= ILL-011a 2-methyl-l-hydroxybenzene Do.

so 01 1 2 H0 I 2% 011:; CH:

6 N=N ILL-CH3 2-methyl-l-hydroxybenzene Greenish yellow,

0 01 JL 2 HO 1;] H

7 QN=N- ILL CH3 Lmethyl-l-hydroxybenzene Do.

0 01 l no N 

1. A DISPERSE MONOAZO DYESTUFF OF THE FORMULA 